Dimethyl Sulfide-Dimethyl Ether and Ethylene Oxide-Ethylene Sulfide Complexes In- Vestigated by Fourier Transform Microwave Spectroscopy and Ab Initio Calculation

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DIMETHYL SULFIDE-DIMETHYL ETHER AND ETHYLENE OXIDE-ETHYLENE SULFIDE COMPLEXES IN- VESTIGATED BY FOURIER TRANSFORM MICROWAVE SPECTROSCOPY AND AB INITIO CALCULATION YOSHIYUKI KAWASHIMA, YOSHIO TATAMITANI, TAKAYUKI MASE, Applied Chemistry, Kanagawa Institute of Technology, Atsugi, Japan; EIZI HIROTA, The Central Office, The Graduate University for Ad- vanced Studies, Hayama, Kanagawa, Japan. The ground-state rotational spectra of the dimethyl sulfide-dimethyl ether (DMS-DME) and the ethylene oxide and ethylene sulfide (EO-ES) complexes were observed by Fourier transform microwave spectroscopy, and a-type and c-type transitions were assigned for the normal, 34S, and three 13C species of the DMS-DME and a-type and b-type rotational transitions for the normal, 34S, and two 13C species of the EO-ES. The observed transitions were analyzed by using an S-reduced asymmetric-top rotational Hamiltonian. The rotational parameters thus derived for the DMS-DME were found consistent with a structure of Cs symmetry with the DMS bound to the DME by two C-H(DMS)—O and one S—H- C(DME) hydrogen bonds. The barrier height V 3 to internal rotation of the ”free” methyl group in the DME was determined to be 915.4 (23) cm−1, which is smaller than that of the DME monomer, 951.72 (70) cm−1,a and larger than that of the DME dimer, 785.4 (52) cm−1.b For the EO-ES complex the observed data were interpreted in the terms of an antiparallel Cs geometry with the EO bound to the ES by two C-H(ES)—O and two S—H-C(EO) hydrogen bonds. We have applied a natural bond orbital (NBO) analysis to the DMS-DME and EO-ES to calculate the stabilization energy CT (= ∆Eσσ*), which were closely correlated with the binding energy EB, as found for other related complexes. aY. Niide and M. Hayashi, J. Mol. Spectrosc. 220, 65-79 (2003). bY. Tatamitani, B. Liu, J. Shimada, T. Ogata, P. Ottaviani, A. Maris, W. Caminati, and J. L. Alonso, J. Am. Chem. Soc. 124, 2739-2743 (2002)..

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